A useful approach called the direct random phase
approximation (dRPA) based on the RI approximation is available. This
particular implementation was added by Joonho Lee working with Martin
Head-Gordon.
688
J. Chem. Theory Comput.
(2020),
16,
pp. 243.
Link
RI-dRPA has been applied to the
thermochemistry
298
J. Chem. Theory Comput.
(2018),
14,
pp. 2596.
Link
and non-covalent interaction
problems
863
J. Chem. Theory Comput.
(2020),
16,
pp. 2258.
Link
and often demonstrated superior performance over
RI-MP2. In terms of the computational cost, RI-dRPA should be compared to the
scaled-opposite-spin MP2 while theoretically it involves diagrams far beyond
second-order and includes infinite-order diagrams similarly to coupled-cluster
theory. In fact, one can view dRPA as a reduced coupled-cluster with doubles
approach.
1074
J. Chem. Phys.
(2008),
129,
pp. 231101.
Link
In a nutshell, we define the dRPA energy as
(6.27) |
where using the plasmon formula we compute
323
J. Chem. Phys.
(2010),
132,
pp. 234114.
Link
(6.28) |
where
(6.29) |
with
(6.30) | ||||
(6.31) |
In this form, the cost of computing the dRPA correlation is quartic-scaling which is comparable to SOS-MP2. To use this method, one must set METHOD = RIDRPA along with AUXBASIS.